CN108912043A - A kind of synthetic method of 2,3,5- trichloropyridine - Google Patents
A kind of synthetic method of 2,3,5- trichloropyridine Download PDFInfo
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- CN108912043A CN108912043A CN201811011295.7A CN201811011295A CN108912043A CN 108912043 A CN108912043 A CN 108912043A CN 201811011295 A CN201811011295 A CN 201811011295A CN 108912043 A CN108912043 A CN 108912043A
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a kind of synthetic method of 2,3,5- trichloropyridines, this method is mainly included the following steps that：(1) 2,3,5- trichlorine 6- is hydrated the synthesis of hydrazino pyridine：Using 2,3,5,6-TCP as raw material, hydrazine hydrate and reaction dissolvent are added into the raw material, reacts certain time at a certain temperature, by processing, obtains 2,3,5- trichlorine 6- hydration hydrazino pyridine；(2) 2,3,5- trichlorine 6- hydration hydrazino pyridine and aqueous sodium hypochlorite solution are obtained in step (1) in alkaline environment, react certain time under certain temperature, by processing, 2,3 are obtained, 5- trichloropyridine crude product obtains target product by vacuum distillation.In synthetic method of the invention reaction raw materials price it is lower and without severe toxicity, it is nonirritant, the Industrial " three Waste " of generation is few, synthetic method is environmentally protective；React relatively thorough, process control is simple, and product yield is high.
Description
Technical field
The invention belongs to pesticide chemical fields, and in particular to the synthetic method of one kind 2,3,5- trichloropyridine.
Background technique
2,3,5- trichloropyridines are important fine-chemical intermediate, are widely used in medicine and pesticide research field.2,
3,5- trichloropyridines react preparation 3,5- dichloro-2-pyridyl phenol with alkali metal hydroxide, are synthetic insecticide mite and herbicide
The important source material of the series pesticides such as Evil grass ether.2,3,5- trichloropyridine can also synthesize 2,3- bis- with further progress fluorination reaction
Fluoro- 5- chloropyridine, the latter are the basic materials for synthesizing herbicide clodinafop-propargyl.
Currently, the synthetic method report of 3,5- trichloropyridines is not very much, to be mainly the following about 2：(1) patent
WO0155-11 is disclosed using penta chloropyridine as raw material, and dechlorination reaction is carried out in the presence of excessive zinc powder and synthesizes 2,3,5- trichlorine pyrroles
The method of pyridine.This method has the drawback that raw material is not easy to obtain, and does not have " Atom economy ".Meanwhile zinc powder is a large amount of
It uses so that the technique does not have cost advantage, metallic zinc is difficult and seriously polluted.(2) 201410669523.5 disclosure of patent
2- chloropyridine, which is reacted with water or alcohols under base catalysis, generates 2- alkoxy pyridines, and 2- alkoxy pyridines are in base
The chloro- 2- alkoxy pyridines of 3,5- bis- are generated with chlorination reaction, last chlorination obtains 2,3,5- trichloropyridines.Synthetic method step
Rapid cumbersome, generation Industrial " three Waste " is relatively more, is not suitable for industrialized production.(3) United States Patent (USP) US 4245098 discloses one kind
It is catalyzed the technology that cyclization method synthesizes 2,3,5- trichloropyridines, mainly includes using trichloroacetaldehyde and acrylonitrile as raw material, in catalyst
Under the action of, prepare 2,3,5- trichloropyridine.Synthesis technology operation is more loaded down with trivial details, and reaction condition is also more harsh, not easily-controllable
System, and it to be applied to a large amount of metal salt, it pollutes the environment, while product yield is also undesirable.
The present invention provides a kind of reaction raw materials without severe toxicity, it is nonirritant, reaction condition is mild, the green ring of process route
It protects, and the synthetic method that by-product is few.
Summary of the invention
Aiming at the shortcomings in the prior art, it is an object of the present invention to provide a kind of synthetic methods of 2,3,5- trichloropyridines.
To achieve the goals above, the present invention adopts the following technical scheme that：
The synthetic method of one kind 2,3,5- trichloropyridine, synthetic route are as follows：
It mainly includes the following steps that：
(1) 2,3,5- trichlorine 6- is hydrated the synthesis of hydrazino pyridine：Using 2,3,5,6-TCP as raw material, to the raw material
Middle addition hydrazine hydrate and reaction dissolvent, react certain time at a certain temperature, by processing, obtain 2,3,5- trichlorine 6- hydrazine hydrates
Yl pyridines；
(2) 2,3,5- trichlorine 6- hydration hydrazino pyridine and aqueous sodium hypochlorite solution are obtained in step (1) in alkaline environment,
Certain time is reacted under certain temperature, by processing, obtains 2,3,5- trichloropyridine crude products；
(3) 2,3,5- trichloropyridine crude products obtained in step (2) obtain target product 2,3,5- by vacuum distillation
Trichloropyridine.
The molar ratio of 2,3,5,6- 4 chloro pyridine and hydrazine hydrate is 1 in step (1):1~1:1.5；Preferred molar ratio is 1:
1.1~1:1.15.
Reaction dissolvent in step (1) is methanol, ethyl alcohol, acetone, 1,2- dichloroethanes, methylene chloride, appointing in toluene
It is a kind of；It is preferred that methanol.
The molar ratio of 2,3,5,6- 4 chloro pyridine and reaction dissolvent in step (1) is 1:1~1:1.5.
Reaction temperature is 25~65 DEG C in step (1), and the reaction time is 1 hour~3 hours；Preferable reaction temperature be 60~
65 DEG C, preferred reaction time is 2 hours.
It is 1 that 2,3,5- trichlorine 6-, which is hydrated hydrazino pyridine and the molar ratio of aqueous sodium hypochlorite solution, in step (2):1~1:
2.5；Preferred molar ratio is 1:1.2~1:1.22.
Sodium hydroxide, potassium hydroxide water, sodium carbonate, potassium carbonate in step (2), sodium bicarbonate；It is preferred that alkaline solution is hydrogen
Sodium oxide molybdena.
Reaction temperature is 40~100 DEG C in step (2), and the reaction time is 1 hour~3 hours；Preferable reaction temperature is 70
~75 DEG C, preferred reaction time is 1 hour.
Processing step in step (1) is：It is cooled to 0~5 DEG C, is stirred 1 hour, filtering.
Processing step in step (2) is：Reaction temperature is now down to 5~10 DEG C, is stirred 1 hour, filtering.
Compared with prior art, the present invention has following advantages：
1. easily buying, price are lower for raw material 2,3,5,6-TCP and hydrazine hydrate etc. in synthetic method of the invention；
2. reacting relatively thorough, process control is simple, and product yield is high；
3. reaction raw materials without severe toxicity, it is nonirritant, the Industrial " three Waste " of generation is few, synthetic method is environmentally protective.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Embodiment 1
The addition 60g methanol into 1000mL four-hole boiling flask, investment 100g 2,3,5,6-TCP, 31.7g hydrazine hydrate,
60~65 DEG C are warming up to, insulation reaction about 2 hours, reaction terminated, and was cooled to 0~5 DEG C, stirred 1 hour, filtering, and solid is
2,3,5- trichlorine 6- are hydrated hydrazino pyridine, and drying obtains white solid 101.6g, yield 96%, content 98.5%.
2,3,5- trichlorine 6- of 100g is added into 1000ml four-hole bottle and is hydrated hydrazino pyridine, 5% sodium hydroxide of 50g content
Aqueous solution is warming up to 70~75 DEG C, and the aqueous sodium hypochlorite solution of 387.6g content 10% is added dropwise, and keeps the temperature 70~75 DEG C, reaction 1 is small
When, reaction terminates, and is cooled to 5~10 DEG C, stirs 1 hour, 2,3,5- trichloropyridine crude products are obtained by filtration, and is evaporated under reduced pressure, obtains
Product is faint yellow solid, yield：95%, content：98%.
Embodiment 2
The addition 50g methanol into 1000mL four-hole boiling flask, investment 100g 2,3,5,6-TCP, 34.6g hydrazine hydrate,
55~60 DEG C are warming up to, insulation reaction about 2 hours, reaction terminated, and was cooled to 0~5 DEG C, stirred 1.5 hours, filtering, and solid is
It is 2,3,5- trichlorine 6- hydration hydrazino pyridine, drying obtains white solid 101.5g, yield 95.8%, content 98.5%.
2,3,5- trichlorine 6- of 100g is added into 1000ml four-hole bottle and is hydrated hydrazino pyridine, 5% sodium hydroxide of 45g content
Aqueous solution is warming up to 70~75 DEG C, and the aqueous sodium hypochlorite solution of 355.3g content 10% is added dropwise, and keeps the temperature 70~75 DEG C, reaction 1 is small
When, reaction terminates, and is cooled to 5~10 DEG C, stirs 1 hour, 2,3,5- trichloropyridine crude products are obtained by filtration, and is evaporated under reduced pressure, obtains
Product is faint yellow solid, yield：93%, content：98%.
Embodiment 3
The addition 60g methanol into 1000mL four-hole boiling flask, investment 100g 2,3,5,6-TCP, 33.1g hydrazine hydrate,
60~65 DEG C are warming up to, insulation reaction about 2 hours, reaction terminated, and was cooled to 0~5 DEG C, stirred 1 hour, filtering, and solid is
2,3,5- trichlorine 6- are hydrated hydrazino pyridine, and drying obtains white solid 101.6g, yield 96%, content 98.4%.
2,3,5- trichlorine 6- of 100g is added into 1000ml four-hole bottle and is hydrated hydrazino pyridine, 5% sodium hydroxide of 57g content
Aqueous solution is warming up to 70~75 DEG C, and the aqueous sodium hypochlorite solution of 360g content 10% is added dropwise, and keeps the temperature 70~75 DEG C, reaction 1 is small
When, reaction terminates, and is cooled to 5~10 DEG C, stirs 1 hour, 2,3,5- trichloropyridine crude products are obtained by filtration, and is evaporated under reduced pressure, obtains
Product is faint yellow solid, yield：94.5%, content：98%.
Embodiment 4
The addition 50g methanol into 1000mL four-hole boiling flask, investment 100g 2,3,5,6-TCP, 36.02g hydrazine hydrate,
60~65 DEG C are warming up to, insulation reaction about 2 hours, reaction terminated, and was cooled to 0~5 DEG C, stirred 1.5 hours, filtering, and solid is
It is 2,3,5- trichlorine 6- hydration hydrazino pyridine, drying obtains white solid 101.5g, yield 95.8%, content 98.7%.
2,3,5- trichlorine 6- of 100g is added into 1000ml four-hole bottle and is hydrated hydrazino pyridine, 5% sodium hydroxide of 45g content
Aqueous solution is warming up to 70~75 DEG C, and the aqueous sodium hypochlorite solution of 345g content 10% is added dropwise, and keeps the temperature 70~75 DEG C, reaction 1.5 is small
When, reaction terminates, and is cooled to 5~10 DEG C, stirs 1 hour, 2,3,5- trichloropyridine crude products are obtained by filtration, and is evaporated under reduced pressure, obtains
Product is faint yellow solid, yield：92.4%, content：98%.
Comparative example 1
The penta chloropyridine for weighing 0.1mol is dissolved in 50ml toluene, then with a certain amount of zinc powder, 4 bromide and
Certain density sodium hydroxide be placed in together equipped with mechanical stirring, thermometer, reflux condensing tube three-necked flask in, start stirring
It is warming up to certain temperature, stops heating after keeping the temperature several hours, cooling, filter, wash filter cake 3-4 times with toluene, merging filtrate,
Toluene is removed under reduced pressure, obtains crude product.When using the experiment condition optimized as follows：Concentration is used to make for the NaOH solution of 8mol/L
It is n (zinc powder) according to reaction mass molar ratio for reaction medium：N (penta chloropyridine)：N (4 bromide)=3.5:1:
0.05, it is reacted 6 hours at 50 DEG C, obtains 2,3,5- trichloropyridine crude product of target product by filtering, being evaporated under reduced pressure, yield is
73%.
Claims (10)
1. one kind 2,3, the synthetic method of 5- trichloropyridine, which is characterized in that mainly include the following steps：
(1) 2,3,5- trichlorine 6- is hydrated the synthesis of hydrazino pyridine：Using 2,3,5,6-TCP as raw material, add into the raw material
Enter hydrazine hydrate and reaction dissolvent, react certain time at a certain temperature, by processing, obtains 2,3,5- trichlorine 6- hydration diazanyl pyrrole
Pyridine；
(2) 2,3,5- trichlorine 6- hydration hydrazino pyridine and aqueous sodium hypochlorite solution are obtained in step (1) in alkaline environment, centainly
At a temperature of react certain time, by processing, obtain 2,3,5- trichloropyridine crude products, by vacuum distillation, obtain target product；
(3) 2,3,5- trichloropyridine crude products obtained in step (2) obtain 2,3,5- trichlorine of target product by vacuum distillation
Pyridine.
2. according to claim 12, the synthetic method of 3,5- trichloropyridines, which is characterized in that 2,3,5 in step (1),
The molar ratio of 6- 4 chloro pyridine and hydrazine hydrate is 1:1~1:1.5；Preferred molar ratio is 1:1.1~1:1.15.
3. according to claim 12, the synthetic method of 3,5- trichloropyridines, which is characterized in that the reaction in step (1)
Solvent is any one of methanol, ethyl alcohol, acetone, 1,2- dichloroethanes, methylene chloride, toluene；It is preferred that methanol.
4. according to claim 12, the synthetic method of 3,5- trichloropyridines, which is characterized in that 2,3 in step (1),
The molar ratio of 5,6- 4 chloro pyridine and reaction dissolvent is 1:3~1:5.
5. according to claim 12, the synthetic method of 3,5- trichloropyridines, which is characterized in that reaction temperature in step (1)
Degree is 25~65 DEG C, and the reaction time is 1 hour~3 hours；Preferable reaction temperature is 60~65 DEG C, and preferred reaction time is 2 small
When.
6. according to claim 12, the synthetic method of 3,5- trichloropyridines, which is characterized in that 2,3,5- in step (2)
It is 1 that trichlorine 6-, which is hydrated hydrazino pyridine and the molar ratio of aqueous sodium hypochlorite solution,:1~1:2.5；Preferred molar ratio is 1:1.2~
1:1.22。
7. according to claim 12, the synthetic method of 3,5- trichloropyridines, which is characterized in that hydroxide in step (2)
Sodium, potassium hydroxide water, sodium carbonate, potassium carbonate, sodium bicarbonate；It is preferred that alkaline solution is sodium hydroxide.
8. according to claim 12, the synthetic method of 3,5- trichloropyridines, which is characterized in that reaction temperature in step (2)
Degree is 40~100 DEG C, and the reaction time is 1 hour~3 hours；Preferable reaction temperature is 70~75 DEG C, and preferred reaction time is 1 small
When.
9. according to claim 12, the synthetic method of 3,5- trichloropyridines, which is characterized in that the processing in step (1)
Step is：It is cooled to 0~5 DEG C, is stirred 1 hour, filtering.
10. according to claim 12, the synthetic method of 3,5- trichloropyridines, which is characterized in that the processing in step (2)
Step is：Reaction temperature is now down to 5~10 DEG C, is stirred 1 hour, filtering.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112441966A (en) * | 2020-12-09 | 2021-03-05 | 山东省农药科学研究院 | Method for producing 2-chloro-3-trifluoromethylpyridine from 2,3, 6-trichloro-5-trifluoromethylpyridine |
| CN115141140A (en) * | 2022-07-06 | 2022-10-04 | 山东昆达生物科技有限公司 | Synthetic method of 3, 5-dichloropyridine |
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| US4127575A (en) * | 1976-10-20 | 1978-11-28 | The Dow Chemical Company | Preparation of chloro substituted pyridines |
| JPH03200769A (en) * | 1989-12-27 | 1991-09-02 | Daicel Chem Ind Ltd | Preparation of pyridine chloride |
| US5977370A (en) * | 1997-12-16 | 1999-11-02 | Daicel Chemical Industries, Ltd. | Process for preparing pyridine chloride |
| CN102093288A (en) * | 2011-01-11 | 2011-06-15 | 衢州恒顺化工有限公司 | Preparation method of trichlorohydrazinopyridine hydrate |
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2018
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4127575A (en) * | 1976-10-20 | 1978-11-28 | The Dow Chemical Company | Preparation of chloro substituted pyridines |
| JPH03200769A (en) * | 1989-12-27 | 1991-09-02 | Daicel Chem Ind Ltd | Preparation of pyridine chloride |
| US5977370A (en) * | 1997-12-16 | 1999-11-02 | Daicel Chemical Industries, Ltd. | Process for preparing pyridine chloride |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112441966A (en) * | 2020-12-09 | 2021-03-05 | 山东省农药科学研究院 | Method for producing 2-chloro-3-trifluoromethylpyridine from 2,3, 6-trichloro-5-trifluoromethylpyridine |
| CN115141140A (en) * | 2022-07-06 | 2022-10-04 | 山东昆达生物科技有限公司 | Synthetic method of 3, 5-dichloropyridine |
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